Intermediates and dyestuffs of the anthraquinone series



, 23 substance of M.

Patented Apr. 24, 1923.

1 rs re FREDERICK WILLIAM ATACK, orraanoansrnn, ENGLAND, AND cr-ramzns WILLIAM scores, or ST. ANDREWS, SCOTLAND.

INTERMEDIATES AND DYESTUFFS No Drawing. Application filed .Tune 3,

To all whom if may concern.

Be it known that we. Funnmncu \VJLLIAM Amen and CHARLES WILLIAM SUUTAR, subjects of the King of Great Britain, residing at Manchester, in the county of Lancaster, England, and St. Andrews, Scotland, res 'iectively, have invented certain new and useful Improvements in Intermediates and Dyestuffs of the Anthraquinone Series, of

which the following is a specification.

This invention relates to improvements in intermediates and dyestuffs of the"anthraquinone series. L V

\Vhen Q-aminoanthraquinone is chloril nated in the usual manner, the 1.3-dichloro derivative is obtained. It has now been found that if Z-aminoanthraquinone is treated with chlorine gas in, for example, glacial acetic acid, it is possible to obtain a 3-chloro derivative first.

It has been stated that a 3.ch.loro derivative of 2.aminoanthraquinone has been obtained from aminochlorhenzoylbenzoic acid. and this body was stated to be a simple P. 280283 c, This body is clearly not the same as that produced by us, which shows a M. P. of about 221 (1.; our product has been proved to be the 3.- chloro derivative, So that the body of M. P.

. 280283 C. must have a different constitution.

It has further been found that this body can be converted by treatment with bromine into a previously unknown 2-amino-1-bromo-3-chloro-anthraquinone.

It has .also been found that this bromo derivative can be transformed into a useful vnew";")dyestufi, whose. constitution is defined The "invention therefore includes the preparation of -l-chloro-Q-amino-anthraquinone by direct chl'orii'iation, the preparation of the broino derivative therefrom and the preparation of a dyestuil from said bromo derivative. The invention includes processes in which twoor all of these steps are performed consecutively in a common solvent.

The invention includes cases in which the 30 various bodies contain another substituent group e. g. derivatives of aeylated amino hi1 b'raquinone.

he following examples illustrate the three steps above recited and also a combined prooessbbut it will be appreciated that OF THE ANTHRAQUINONE SERIES.

1921. Serial No. 474,757.

equivalents may be employed for the reagents and steps which are enumerated.

Example 1.

Example Chlorine gas was passed at room temporalure nto a suspension or 10 g. 2-aminoantraqume H1 100 nitrobenzenc. which was kept well shaken, until the necessary increase in weight had taken place. The mixture was then boiled vigorously for 1} hour, after standing overnight the 2-amino: 3-chloro-anthraquinone, which had separated in crystalline form, was filtered off, washed with nitrobenzene, alcohol and finally with hot water. Afterdrying, the product had amelting point of 22l-222 G.

This melting point was only very slightly altered by sublinmtion of the product.

Sodium carbonate or otherneutralisim agent may he added ttithe nitrobcnzenei?" desired.

Example 3.

2().parts by weight of 2-amino3-chloroanthrarpiinone and 10 parts by weight of anhydrous sodium carbonate suspended in ISO parts by weight of nitrobenzene were treated with 21 parts by weightof bromine dissolved in 60 parts by weight of nitrobenzene. The bromine solution was added at the ordinary temperature over a period of minutes and the mixture then heated at (.3. for one and a quarter hours. After allowing to stand for several hours the mixture was filtered, washed and .dried. 2- amino-l -bromo- 3-chloro-anthraquinone Was obtained as orange colored needles of melt ing point 235 C.

Example I 4.

10 parts by weight of 2-amino-l-bromo-3- chloro-anthraquinone, 5 ,arts by weight of fused sodium acetate an 3 parts by weight of crystalline copper acetate are heated with 12) parts by weight of nitrobenzene' at the boil until no further d vest-ufi' is produced. After allowing to cool, the dyestuii' was fittered ofl, freed from nitrobenzene and dried. he product dyed cotton bright blue shades from a ll \"dl.()Slllpl1ll;Q vat. The product appears to be 3.3-dichloro-anthraquinone-1.2.2 lN-dihydro-azine, but it is possible that the amine (as distinguished from hydroazine) may be present. Other inert solvents may be used e4. o.nitrotoluene.

The following example illustrates a process in which the reactions are performed consecutively in a common liquid medium without isolation of intermediate products.

parts by weight of Z-amino-anthraquinone, suspended in 200 parts of nitrobenzene, are treated with chlorine until the necessary increase in weight has taken place, the mixture is then boiled for 1'; hours. 28 parts of bromine. dissovled in 30 parts of nit-robenzcne added at the ordinary temperature over a period oi 30 minutes. After h parts of anhydrous sodium carbonate have been added the mixture is heated at 100 C for 1 hour, at 150? t. for 1 hour and finally raised to boiling.

parts of anlrrdrous sodium acetate and 10 parts of copper acetate are added and the mixture boiled under a reflux condenser, until dyestufi is no longer produced.

The dystufi" is filtered trom the warm solution, freed from nitrobenzene and dried. The product dj'es cotton bright blue shades from a hydrosulphite vat.

W e declare that what we claim is 1. The process of preparing a new dyestull which consists in condensing 2.ami.no. l.b101110.3.chloro.anth aquinone.

2. The. process of preparing a new dyestutt which consists in limited chlorination of 2.amino.anthraquinone, bromination of 2.amino.3.chloroanthraquinone and condensation oi 2.11mlnolbromo.3.chloro.a.nthraquinone wherein at least two of said operations are performed mmsecutively in a corn mon liquid without isolation of the intermediate PTOdllC-t.

3. As anew product, the dyestuil 3.3- dichloro anthraquinone 1.2.2.l. N dihy-droazine;

The process of preparing a new dyestuflt which consists in condensing a body containing the grouping in witness whereof, we have hereunto signed our names this 13th day of May 1921, in the presence of two subscrmmgwitnesses. 

